Establishing Li-acetylide (Li2C2) as functional element in solid-electrolyte interphases in lithium-ion batteries

Abstract

Previously, lithium-acetylide (Li₂C₂) had been identified as electrolyte degradation product on lithium-metal based electrodes using Raman spectroscopy. This raised the question, if Li₂C₂ is also be formed on graphitic electrodes in lithium-ion batteries without lithium metal present. In order to shed light on this research question, we performed a series of in situ Raman experiments with graphitic electrodes in half- and full-cell configuration. The recorded cell potential dependent spectra clearly prove the presence of Li₂C₂ in the lithiated state of the electrodes, but the according peak vanishes when delithiating. This observation indicates a somewhat reversible process involving Li₂C₂. Several chemical/electrochemical reactions are in question to contribute to this effect. With respect to its properties and potential role in the solid-electrolyte interphase (SEI) DFT calculations of Li₂C₂-nanoclusters were performed, which revealed an exceptionally low energy band gap, hence a remarkable electric conductivity. In conjunction with a relatively high ionic conductivity, Li₂C₂ appears to play a key role in the degradation of lithium-ion batteries, which had not yet been revealed nor taken into account in simulations of the interphase.